Incidental ingestion of Chromite ore processing residue (COPR) particles poses a potential health risk. The purpose of this study was to determine the Cr bioaccessibility from COPR using the in vitro gastrointestinal (IVG) procedure. The bioaccessible Cr(VI) was 53.8% and 42.9%, respectively, in the gastric and intestinal phases from a total of 19490mgkg(-1) Cr(VI) in COPR. Food intake including milk, dough, and ascorbic acid resulted in a significant decrease in Cr(VI) bioaccessibility. Some organic acids such as lactic, malic, and citric acid moderately reduced Cr(VI), while acetic acid exhibited no capacity for Cr(VI) reduction. The integrated area under the concentration-time curve (AUC) of the IVG extraction was used to calculate bioaccessibility. Compared with the bioaccessibility conventionally estimated using concentrations at the end of the extraction (CEP), the AUC technique should be implemented to confirm the accuracy of the IVG method when reduction of Cr(VI) occurs during the extraction. The absence of Cr(VI) phases in extracted residues as evidenced by XANES and XRPD analysis confirmed the Cr(VI) release and Cr(VI) reduction by food and ascorbic acid. With readily bioaccessible Cr(VI) and rapid human uptake, reduction of Cr(VI) might not be as effective a detoxification pathway as initially thought.